Molecular Structure and Bonding- 2. Assis.Prof.Dr.Mohammed Hassan Lecture 3
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1 Molecular Structure and Bonding- 2 Assis.Prof.Dr.Mohammed Hassan Lecture 3
2 Hybridization of atomic orbitals Orbital hybridization was proposed to explain the geometry of polyatomic molecules. Covalent bonding was presumed to arise due to the overlap of atomic orbitals and the sharing of electron pairs. Linear sp hybrids. These are composed of the valence shell s-orbital and one of the three p-orbitals. The other two p-orbitals remain unhybridized and may hold lone pairs or participate in p-bonding. The two equivalent sp hybrid orbitals pointat 180 o to each other and their formation is depicted graphically and mathematically below:
3 Acetylene or ethyne C2H2
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5 Trigonal sp 2 hybrids. These are composed of the valence shell s-orbital and two of the p-orbitals, say the p x and p y to produce a set of hybrids directed in the xy plane at 120 o to each other. The p z orbital will be left to hold a lone pair or participate in p-bonding. The diagram below shows the 2s, 2p x and 2p y orbitals superimposed in the same space before hybridization.
6 Ethylene or ethyene C2H4
7 Tetrahedral sp 3 hybrids. These are composed of the valence shell s-orbital and all three p-orbitals. The diagram below shows these superimposed in the same space before hybridization.
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9 Iodine pentafluoride - IF 5 atm. No. I=53. F=9
10 Carbonyl Chloride (Phosgene) - COCl2
11 Sulphate - SO 4 2- S=16)
12 Molecular Orbitals Just as the valence electrons of atoms occupy atomic orbitals (AO), the shared electron pairs of covalently bonded atoms may be thought of as occupying molecular orbitals (MO). It is convenient to approximate molecular orbitals by combining or mixing two or more atomic orbitals. In general, this mixing of n atomic orbitals always generates n molecular orbitals. The hydrogen molecule provides a simple example of MO formation. In the following diagram, two 1s atomic orbitals combine to give a sigma (σ) bonding (low energy) molecular orbital and a second higher energy MO referred to as an antibonding orbital. The bonding MO is occupied by two electrons of opposite spin, the result being a covalent bond.
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16 Phosphorus Pentachloride
17 Molecules and Ions with double bonds
18 IONIC OR ELECTROVALENT BOND From the Kössel and Lewis treatment of the formation of an ionic bond, it follows that the formation of ionic compounds would primarily depend upon: The ease of formation of the positive and negative ions from the respective neutral atoms; The arrangement of the positive and negative ions in the solid, that is, the lattice of the crystalline compound. The formation of a positive ion involves ionization, i.e., removal of electron(s) from the neutral atom and that of the negative ion involves the addition of electron(s) to the neutral atom.
19 Most ionic compounds have cations derived from metallic elements and anions from non-metallic elements. The ammonium ion, NH 4 + (made up of two nonmetallic elements) is an exception. It forms the cation of a number of ionic compounds. Polarity of Molecules The "charge distribution" of a molecule is determined by The shape of the molecule The polarity of its bonds
20 A Polar Molecule: The center of the overall negative charge on the molecule does not coincide with the center of overall positive charge on the molecule The molecule can be oriented such that one end has a net negative charge and the other a net positive charge, i.e. the molecule is a dipole A Nonpolar molecule Has no charges on the opposite ends of the molecule Or, has charges of the same sign on the opposite ends of the molecule Molecule is not a dipole
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22 HYDROGEN BONDING Nitrogen, oxygen and fluorine are the higly electronegative elements. When they are attached to a hydrogen atom to form covalent bond, the electrons of the covalent bond are shifted towards the more electronegative atom. This partially positively charged hydrogen atom forms a bond with the other more electronegative atom. This bond is known as hydrogen bond and is weaker than the covalent bond. For example, in HF molecule, the hydrogen bond exists between hydrogen atom of one molecule and fluorine atom of another molecule as depicted below : H δ+ F δ H δ+ F δ H δ+ F δ
23 Types of H-Bonds (1) Intermolecular hydrogen bond : It is formed between two different molecules of the same or different compounds. For example, H-bond in case of HF molecule, alcohol or water molecules, etc. (2) Intramolecular hydrogen bond : It is formed when hydrogen atom is in between the two highly electronegative (F, O, N) atoms present within the same molecule. For example, in o-nitrophenol the hydrogen is in between the two oxygen atoms.
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25 van der Waals force Relatively weak electrical forces that attract neutral (uncharged) molecules to each other in gases, liquefied and solidified gases, and almost all organic liquids and solids. Solids held together by van der Waals forces typically have lower melting points and are softer than those held together by ionic, covalent, or metallic bonds ( bonding). The forces arise because neutral molecules, though uncharged, are usually electric dipoles, which have a tendency to align with each other and to induce further polarization in neighbouring molecules, resulting in a net attractive force. They are somewhat weaker than the forces involved in hydrogen bonding.
26 EXERCISES 1-Write Lewis dot symbols for atoms of the following elements : Mg, Na, B, O, N, Br. 2-Write Lewis symbols for the following atoms and ions: S and S 2- ; Al and Al 3+ ; H and H - 3-Draw the Lewis structures for the following molecules and ions : H 2 S, SiCl 4, BeF 2, CO 3 2, HCOOH 4-Write the favourable factors for the formation of ionic bond 5-Explain the important aspects of resonance with reference to the CO Explain with the help of suitable example polar covalent bond.
27 7-Which out of NH 3 and NF 3 has higher dipole moment and why. 8-What is meant by hybridisation of atomic orbitals? Describe the shapes of sp, sp 2, sp 3 hybrid orbitals. 9-Describe the change in hybridisation (if any) of the Al atom in the following reaction. AlCl 3 + Cl AlCl 4 10-Draw diagrams showing the formation of a double bond and a triple bond between carbon atoms in C 2 H 4 and C 2 H 2 molecules. 11-What is the total number of sigma and pi bonds in the following molecules? (a) C 2 H 2 (b) C 2 H 4
28 12-Which hybrid orbitals are used by carbon atoms in the following molecules? CH 3 -CH 3 ; (b) CH 3 -CH=CH 2 ; (c) CH 3 -CH 2 -OH; (d) CH 3 -CHO (e) CH 3 COOH. 13-What do you understand by bond pairs and lone pairs of electrons? Illustrate by giving one exmaple of each type. 14-Describe the hybridisation in case of PCl5. Why are the axial bonds longer as compared to equatorial bonds? 15-Define hydrogen bond. Is it weaker or stronger than the van der Waals forces? 16-What is an ionic bond? With two suitable examples explain the difference between an ionic and a covalent bond? 17-Predict the hybridisation of each carbon in the molecule of organic compound given below. Also indicate the total number of sigma and pi bonds in this molecule.
29 18-Group the following as linear and non-linear molecules : H 2 O, HOCl, BeCl 2, Cl 2 O. 19-Predict the shapes of the following molecules on the basis of hybridisation. BCl 3, CH 4, CO 2, NH 3.
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